Session A36: Focus Session: New Energy I

Facing our Energy Challenges in a New Era of Science

As our nation and the world face daunting challenges in energy supply and the environmental consequences of energy use, how can basic science contribute to transforming the way in which we generate and use energy? How can we use the power of modern science, notably chemical physics, to accelerate the transition to a more sustainable energy future? In this talk, I shall present some of the current strategic thinking from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (BES). In particular, I shall present how the department is approaching the entire R{\&}D spectrum for energy technologies and how BES engages the scientific community to identify basic research needs for advancing energy technologies.   

Semiconductor nanostructures for artificial photosynthesis

Nanowires, with their unique capability to bridge the nanoscopic and macroscopic worlds, have already been demonstrated as important materials for different energy conversion. One emerging and exciting direction is their application for solar to fuel conversion. The generation of fuels by the direct conversion of solar energy in a fully integrated system is an attractive goal, but no such system has been demonstrated that shows the required efficiency, is sufficiently durable, or can be manufactured at reasonable cost. One of the most critical issues in solar water splitting is the development of a suitable photoanode with high efficiency and long-term durability in an aqueous environment. Semiconductor nanowires represent an important class of nanostructure building block for direct solar-to-fuel application because of their high surface area, tunable bandgap and efficient charge transport and collection. Nanowires can be readily designed and synthesized to deterministically incorporate heterojunctions with improved light absorption, charge separation and vectorial transport. Meanwhile, it is also possible to selectively decorate different oxidation or reduction catalysts onto specific segments of the nanowires to mimic the compartmentalized reactions in natural photosynthesis. In this talk, I will highlight several recent examples in this lab using semiconductor nanowires and their heterostructures for the purpose of direct solar water splitting.   

Oxygen Evolution Electrocatalysis on Cobalt Oxide surfaces

The oxidation of water for hydrogen production using sunlight is of high importance to photo-fuel cell research. The electrochemical approach via heterogeneous catalysis to water splitting is a very promising route. The key challenge of this method lies in reduction of the loses, i.e., over-potential, for the oxygen evolution reaction (OER) on the anode. In this work, we investigate the dependence of theoretical over-potential of OER on type of anode by applying standard density functional theory (DFT). We attempt to explain recent experimental observation of enhanced activity on gold supported Cobalt Oxide surfaces [1]. We explore variety of possible CoO structures and associated surfaces which could emerge under operating conditions of catalyst. Finally, we also explore the influence of environment and admixtures of CoO with other elements. \\[4pt] [1] B.S. Yeo, A.T. Bell, AT, J. Am. Chem. Soc., 133, 5587-5593 (2011).   

High-throughput synthesis and screening of photon absorbers and photocatalysts for solar fuel cells

Joint Center for Artificial Photosynthesis is a D.O.E. Energy Innovation Hub conceived to develop solar fuel cell technologies by bringing together the critical mass of scientist and engineers nationwide. The High-Throughput Experimentation group at JCAP is developing pipelines for accelerated discovery of new materials - photon absorbers, photoelectrochemical and electrochemical catalysts - using combinatorial approaches (ink-jet, sol-gel, physical vapor deposition). Thin films of semiconducting metal-oxides, sulfides, nitrides and phosphides are synthesized and screened in high-throughput according to their optical and photoelectrochemical properties, as well as structure and phase. Vast libraries of materials and data are generated and made available to inside and outside research groups. Here we present data on binary, ternary and quaternary metal-oxide systems prepared by the ink-jet technology. The systems include tungsten-based photo-absorbers and nickel-iron-based catalysts for water splitting.   

Transport in and chemistry on transition metal oxides for energy conversion

We use quantum mechanics techniques to search for robust, efficient, and inexpensive materials for solid oxide fuel cells (SOFCs) that convert fuels to electricity, photovoltaics (PVs) that convert sunlight to electricity, and photo-catalytic electrodes (PCEs) that convert sunlight, CO$_{2}$, and H$_{2}$O into fuels. In our SOFC research, we focus on cathode optimization, often considered the limiting factor. If oxide ion diffusion and electron transport can be enhanced, along with rapid dissociative adsorption of dioxygen, lower temperatures can be used, which would facilitate wider deployment. In the solar energy conversion arena, the cost-efficiency tradeoff for PV materials motivates new options. I will discuss why it is difficult to find effective PCE materials; in particular I will enumerate the very significant constraints beyond those on PVs that they must satisfy to achieve high efficiency. Limiting oneself to abundant elements further constrains the design space. As a result, we are focusing primarily on first row transition metal oxide materials. Key properties of conventional and novel materials, along with some new design principles, will be discussed. The work is revealing which dopants or mixed oxides are likely to provide the most efficient energy conversion materials.   

A comparison in activity between transition-metal oxides and transition metals

Transition-metal oxides are widely used materials in catalysis as substrates and promoters, but also as the active catalyst materials themselves. We compare the reactivity of transition-metal oxides with the one of transition metals. The comparison is exemplified for the ammonia synthesis reaction. First we show that there exist characteristic Br{\o}nsted-Evans Polanyi (BEP) relations (linear relations between transition state and dissociation energies) for dissociation of molecules on transition-metal oxides in the rutile and perovskite structure. It is well-known that the (211) metal surface is several orders of magnitude more reactive than the (111) metal surface due to the lower BEP line for the 211 facet. We find that both rutiles and perovskites follow BEP relations that are lower than the one of the 211 facet. Second we utilize the established BEP relations together with calculated adsorption energetics in a micro-kinetic model to obtain a volcano plot for the catalytic activity. We find that oxides have a higher turn over frequency as compared with metals. Hence, oxides intrinsically have a great advantage in terms of catalytic activity which opens up for catalyst design.   

Energy conversion and fuel production from electrochemical interfaces

Design and synthesis of energy efficient and stable electrochemical interfaces (materials and double layer components) with tailor properties for accelerating and directing chemical transformations is the key to developing new alternative energy systems -- fuel cells, electrolizers and batteries. In aqueous electrolytes, depending on the nature of the reacting species, the supporting electrolyte, and the metal electrodes, two types of interactions have traditionally been considered: (i) direct -- covalent {\-} bond formation between adsorbates and electrodes, involving chemisorption, electron transfer, and release of the ion hydration shell; and (ii) relatively weak non-covalent metal-ion forces that may affect the concentration of ions in the vicinity of the electrode but do not involve direct metal-adsorbate bonding. The range of physical phenomena associated with these two classes of bonds is unusually broad, and are of paramount importance to understand activity of both metal-electrolyte two phase interfaces and metal-Nafion-electrolyte three phase interfaces. Furthermore, in the past, researcher working in the field of fuel cells (converting hydrogen and oxygen into water) and electrolyzers (splitting water back to H$_{2}$ and O$_{2})$ ) seldom focused on understanding the electrochemical compliments of these reactions in battery systems, e.g., the lithium-air system. In this lecture, we address the importance of both covalent and non-covalent interactions in controlling catalytic activity at the two-phase and three-phase interfaces. Although the field is still in its infancy, a great deal has already been learned and trends are beginning to emerge that give new insight into the relationship between the nature of bonding interactions and catalytic activity/stability of electrochemical interfaces. In addition, to bridge the gap between the ``water battery'' (fuel cell $\leftrightarrow $ electrolyzer) and the Li-air battery systems we demonstrate that this would require fundamentally new knowledge in several critical areas. We conclude that understanding the complexity (simplicity) of electrochemical interfaces would open new avenues for design and deployment of alternative energy systems.